TECHNICAL FIELD
[0001] The present invention relates to a composite separation membrane which has excellent
chemical resistance, separation performance, and water permeability.
BACKGROUND ART
[0002] Conventionally, separation membranes which have been used industrially include an
asymmetric membrane from cellulose acetate (for example, Patent Document 1). However,
this membrane has problems with hydrolysis resistance, microbial resistance, etc.,
and is also insufficient in salt removal rate and water permeability. Therefore, the
cellulose acetate asymmetric membrane has not been put to practical use yet in a wide
range of applications, while the membrane has been used for some applications.
[0003] In order to correct these defects, a composite separation membrane which has a porous
membrane coated with a separation function layer which is a different material and
substantially responsible for membrane separation performance has been created as
a separation membrane which differs from the asymmetric membrane in terms of configuration.
In the case of the composite separation membrane, it is possible to select an optimum
material for each of the separation function layer and the microporous supporting
membrane, and a variety of methods can also be selected for the membrane forming technique.
Most of composite separation membranes which are currently commercially available
have a monomer subjected to interfacial polycondensation on a porous membrane, and
a polyamide is used for the separation function layer. Specific examples thereof include
Patent Document 2.
[0004] These composite separation membranes provide higher desalination performance, and
higher water permeability at the same time, than the cellulose acetate asymmetric
membrane. However, such a composite separation membrane using a polyamide includes
an amide linkage in its main chain, and thus still has insufficient chemical resistance,
and it is known that the desalination performance and selective separation performance
are significantly degraded due to a treatment with chlorine, hydrogen peroxide, etc.,
for use in sterilization of the membrane.
[0005] In that regard, for example, in Patent Document 3 and Patent Document 4, while studies
are made on a separation function layer obtained by polymerizing a vinyl based compound,
which has high general versatility for the membrane forming technique and has a wide
range of selectivity for raw materials. However, the composite separation membrane
produced with the use of a vinyl based compound as described above has excellent chemical
resistance, it can hardly be said that either water permeability or separation performance
is sufficient.
[0006] On the other hand, in Patent Document 5, Patent Document 6, Patent Document 7, and
Non-Patent Document 1, techniques are known for forming space in a membrane containing
therein a polyhedral silsesquioxane which has a three-dimensionally steric structure,
and for example, Patent Document 5 discloses a multi-layer film with a polyhedral
silsesquioxane containing membrane formed on a transparent base material; likewise,
Patent Document 6 discloses a gas separation membrane which has a polyhedral silsesquioxane
mixed with a single-layer gas separation membrane made of a resin; Patent Document
7 discloses a filtration medium which has a base material coated with a polyhedral
silsesquioxane containing polymer; and Non-Patent Document 1 discloses a gas separation
membrane with a polyhedral silsesquioxane introduced into polystyrene. However, the
gas separation membranes described above which have significantly low water permeability
are not able to be used as separation membranes for water treatments, because separation
membranes for water treatments are required to satisfy all of water permeability,
separation performance, and physical durability and chemical durability.
[Patent Document 1]
U.S. Patent No. 3,133,132
[Patent Document 2]
U.S. Patent No. 4,277,344
[Patent Document 3] Japanese Patent Application Laid-Open No.
2000-117077
[Patent Document 4] Japanese Patent Application Laid-Open No.
2004-17002
[Patent Document 5] Japanese Patent Application Laid-Open No.
2000-334881
[Patent Document 6] Japanese Patent Application Laid-Open No.
2008-530312
[Patent Document 7] Japanese Patent Application Laid-Open No.
2008-515668
[Non-Patent Document 1]
H. Ríos-Dominguez, another three, "Journal of Membrane Science", 271, (2006), p. 94-100
DISCLOSURE OF THE INVENTION
Problem to be solved by the invention
[0007] Therefore, an object of the present invention is to obtain a composite separation
membrane which has excellent chemical resistance and satisfies high separation performance
and high water permeability.
Means for solving the problem
[0008] The present invention for solving the problem described above is achieved by the
following aspects (1) to (4).
- (1) A composite separation membrane having a separation function layer on a porous
supporting membrane, characterized in that the separation function layer contains
at least a polymer of a polyhedral silsesquioxane represented by the following general
formula (a) and a hydrophilic monomer.
(R1SiO1.5)n(R2SiO1.5)m General Formula (a)
(In the formula, R1 includes a polymerizable reactive moiety; R2 represents a hydrogen atom or an alkyl group, which may be substituted with a substituent;
and n and m each represent an integer satisfying n ≥ 2 and m ≥ 0, with n + m being
8, 10 or 12.)
- (2) The composite separation membrane according to (1), wherein the porous supporting
membrane has an average pore size of 1 to 100 nm.
- (3) The composite separation membrane according to (1), wherein the separation function
layer has a thickness of 500 nm or less.
- (4) The composite separation membrane according to (1), wherein the hydrophilic monomer
is an acid monomer.
Advantageous Effect of the Invention
[0009] According to the present invention, a composite separation membrane can be provided
which has excellent chemical resistance and water permeability, and the industrial
improvements of reduction in running cost, reduction in cost, and energy saving are
expected through the use of this membrane.
BEST MODE FOR CARRYING OUT THE INVENTION
[0010] A composite separation membrane according to the present invention includes a separation
function layer which has a fluid separation function such as desalination performance
or water permeability performance and a porous supporting membrane for supporting
the separation function layer.
[0011] The separation function layer is
characterized in that it contains at least a polymer of a polyhedral silsesquioxane represented by the
following general formula (a) and a hydrophilic monomer.
(R
1SiO
1.5)
n(R
2SiO
1.5)
m General Formula (a)
(In the formula, R
1 includes a polymerizable reactive moiety; R
2 represents a hydrogen atom or an alkyl group, which may be substituted with a substituent;
and n and m each represent an integer satisfying n ≥ 2 and m ≥ 0, with n + m being
8, 10 or 12.)
[0012] In the polyhedral silsesquioxane for use in the present invention, the moiety represented
by R
1 represents a reactive moiety which is polymerizable with the hydrophilic monomer.
The polyhedral silsesquioxane bonded to the hydrophilic monomer with two or more (n
≥ 2) reactive moieties interposed therebetween form a cross-linked structure, thereby
resulting in improvement of the resistance to dissolution in a variety of solvents,
in particular, water. In the case of a separation membrane obtained by polymerizing
a hydrophilic monomer singly with a polyhedral silsesquioxane including no reactive
moiety, the structure of the separation membrane is changed by swelling depending
on the hydrophilicity of the hydrophilic monomer, or by elution, and there is thus
concern that the membrane separation performance will be degraded. Therefore, the
separation membrane composed of the polymer of the polyhedral silsesquioxane and hydrophilic
monomer come to have extremely high water permeability performance with a combination
of voids at the molecular level, which derives from the three-dimensionally steric
structure of the polyhedral silsesquioxane, and the improvement in hydrophilicity
with the hydrophilic monomer.
[0013] In the polyhedral silsesquioxane for use in the present invention, the n and m in
the general formula (a) each represent an integer satisfying n ≥ 2 and m ≥ 0, and
the n + m needs to be 8, 10 or 12. The n + m which takes the value of 8, 10 or 12
brings about sufficient homogeneity for the separation function layer and a sufficient
thin film formation property for the separation function layer, and the present invention
thus produces desired effects. In particular, the polyhedral silsesquioxane with n
+ m = 8, which is referred to as T-8 silsesquioxane, produces particularly high effects
from its cubic structure in the present invention, and is thus the most preferable
embodiment.
[0014] In addition, the respective values of the n and m determine the content ratio between
R
1 and R
2 in the polyhedral silsesquioxane. The introduction of R
1 increases the composition ratio of the reactive moiety which is polymerizable with
the hydrophilic monomer, whereas the introduction of R
2 increases the composition ratio of the nonpolymerizable moiety. Thus, the values
of n and m can be appropriately determined depending on desired performance to be
obtained, as long as the n and m satisfy the requirements mentioned above.
[0015] Examples of R
1 include, but not limited to, a vinyl group, a vinyl halide group, a vinyl ester group,
other vinyl derivatives, an acrylic group, a methacrylic group, and other acrylic
derivatives. In addition, among these, compounds containing an acrylic group, a methacrylic
group, or other acrylic derivative are preferable as R
1 in terms of polymerization reactivity, and compounds containing a methacrylic group
which is poorly hydrolyzed are particularly preferable in terms of the chemical durability
of the membrane.
[0016] The alkyl group represented by R
2 may be a straight-chain alkyl group or a branched-chain alkyl group, and may be substituted
with a substituent. Specifically, examples of R
2 include a hydrogen atom, a methyl group, an ethyl group, a cyclopentyl group, a cyclohexyl
group, an isopropyl group, a 2-ethylhexyl group, a 2-chloroethyl group, a methacryloxypropyl
group, an allyl group, a 3-aminopropyl group, a 3-mercaptopropyl group, a 3-glycidoxy
propyl group, and a phenyl group.
[0017] The polyhedral silsesquioxane for use in the present invention may be an article
on the market or can be produced in accordance with a known synthesis method. For
example, a silsesquioxane containing a methacrylic group (n = 8 and m = 0 in the general
formula (a)) is sold as "Methacryl-POSS (registered trademark)" from Sigma-Aldrich
Japan. As the known synthesis method, as described in, for example, Japanese Patent
Application Laid-Open No.
2004-143449, 3-methacryloxy propyl trimethoxysilane is hydrolyzed and partially condensed in
the presence of an polar organic solvent and a basic catalyst, and the hydrolysis
product is further condensed again in the presence of a nonpolar product and a basic
catalyst, thereby allowing the polyhedral silsesquioxane to be obtained.
[0018] The hydrophilic monomer for use in the present invention needs to be a hydrophilic
monomer including a reactive moiety which is able to be bonded to the polymerizable
reactive moiety of the polyhedral silsesquioxane. In addition, the hydrophilic monomer
needs to be a monomer containing a hetero atom in order to increase the selective
water permeability when the composite separation membrane is used for separation of
a solution or the like. This hydrophilic monomer may be a compound of a straight-chain
monomer containing a hetero atom or a compound which has a hetero ring structure.
These hydrophilic monomers may be used singly, or multiple types of the hydrophilic
monomers can be used in combination.
[0019] The hetero atom herein means atoms other than carbon and hydrogen atoms, such as
an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorous atom. Among these
hetero atoms, hydrophilic monomers containing at least one selected from the group
consisting of an oxygen atom, a nitrogen atom, and a sulfur atom are preferable because
the effect described above is extensively produced. In addition, functional groups
containing an atom as mentioned above and highly hydrophilic functional groups include
an alkoxyl group, a carboxyl group, a carbonyl group, a keto group, an ester group,
a carbonate group, an amide group, a sulfone amide group, a cyano group, a formyl
group, a hydroxyl group, a mercapto group, an amino group, an imino group, an alkylthio
group, a sulfinyl group, a sulfonyl group, a sulfo group, a nitro group, a nitroso
group, an ether group, a thioether group, and a phosphoester group.
[0020] Above all, when the long-term stability of the composite separation membrane is considered
in terms of resistance to fouling, the hydrophilic functional group preferably contains
an acid group containing monomer which is an acid group. These acid group containing
monomers are also referred to as acid monomers hereinafter. Preferable acid groups
are a carboxyl group and a sulfo group, and these groups may have an acid form, an
ester for, or a salt form. These monomers can contain two or more acid groups, and
monomers containing one to two acid groups are preferable.
[0021] Preferable monomers containing a carboxyl group includes, for example, a maleic acid,
an acrylic acid, a methacrylic acid, a 2-(hydroxymethyl)acrylic acid, and a 4-vinylbenzoic
acid.
[0022] Preferable monomers containing a sulfo group include, for example, a vinyl sulfonic
acid, a styrenesulfonic acid, or 3-(methacrylamide)propyl sulfonic acid.
[0023] As a method for the polymerization of the polyhedral silsesquioxane and the hydrophilic
monomer, the polymerization can be carried out by a heat treatment, electromagnetic
wave irradiation, electron beam irradiation, exposure to radiation, and plasma irradiation.
The electromagnetic wave herein includes infrared rays, ultraviolet rays, X ray, and
γ ray. While an optimum selection of the polymerization method may be made appropriately
depending on the structure of the monomer, productivity, cost, etc., polymerization
by a heat treatment and electromagnetic waves is preferable in terms of running cost,
etc., and polymerization by infrared rays or ultraviolet rays is more preferable among
electromagnetic waves. In the case of actually carrying out polymerization with the
use of infrared rays or ultraviolet rays, these light sources do not have to selectively
generate these light rays, and it is enough for the light sources to generate light
easy including these electromagnetic ways. However, the strength of these electromagnetic
waves is preferably higher as compared with electromagnetic waves in other wavelength
range, in terms of the ability to reduce the polymerization time and control the polymerization
conditions.
[0024] Further, the electromagnetic waves used for the polymerization can be generated from
a halogen lamp, a xenon lamp, a UV lamp, an excimer lamp, a metal halide lamp, a rare
gas fluorescent lamp, a mercury lamp, etc. While the strength of the electromagnetic
waves is not particularly limited as long as the cross-linking agent and the reactive
monomer can be polymerized with each other, low pressure mercury lamps and excimer
lamps which are capable of short-wavelength ultraviolet irradiation with a high degree
of efficiency are preferable above all because of their high thin film forming properties.
The thickness and form of the polymer according to the present invention may also
vary significantly depending on the respective polymerization conditions, and may
vary significantly depending on the wavelength and intensity of the light, the distance
to an object to be irradiated, the processing time, in the case of polymerization
with electromagnetic waves. Therefore, these conductions need to be appropriately
optimized.
[0025] In addition, it is preferable to add a polymerization initiator, a polymerization
promoter, etc., in the formation of the separation function layer for the purposed
of increasing the polymerization rate. The polymerization initiator and the polymerization
promoter herein are not particularly limited, and appropriately selected depending
on the structures of the polyhedral silsesquioxane and hydrophilic monomer, the polymerization
approach, etc.
[0026] Examples of polymerization initiator suitable for the present invention include benzoin,
benzil ketal, α-hydroxyacetophenone, α-aminoacetophenone and derivatives thereof,
and mixture thereof. Azo compounds (for example, 2,2'-azobis(isobutyronitrile) (AIBN)
or azobis-(4-cyanovalerianic acid)), or peroxides (for example, dibenzoyl peroxide,
lauroyl peroxide, tert-butyl peroctanoate, tert-butyl perbenzoate, or di-(tert-butyl)peroxide),
further aromatic diazonium salts, bis-sulfonium salts, aromatic iodonium salts, potassium
persulfate, ammonium persulfate, etc., are preferable as initiators for thermal curing.
[0027] As the polymerization promoter for accelerating the initiation of the polymerization,
a reducing agent, a hydrogen donor such as amines, alcohols, and ethers, a sensitizing
dye, etc., may be added appropriately.
[0028] The separation function layer according to the present invention is
characterized in that it includes at least a polymer of the polyhedral silsesquioxane and hydrophilic monomer.
The separation function layer according to the present invention may contain compositions
other than the polymer to such an extent that the advantageous effect of the present
invention is not impaired, and for example, a surfactant and a filler may be added.
[0029] The surfactant is not particularly limited, and selected appropriately depending
on the structures of the polyhedral silsesquioxane and hydrophilic monomer, etc.,
for the purpose of providing desired wettability.
[0030] The filler is not particularly limited, and may appropriately contain metal nanoparticles,
organic nanoparticles, for the purpose of improving the mechanical strength of the
composite separation membrane.
[0031] In order to control the thickness of the separation function layer according to the
present invention, it is preferable to add a solvent in the polymerization of the
polyhedral silsesquioxane and hydrophilic monomer. The solvent herein is not particularly
limited as long as the solvent can dilute the mixture of the polyhedral silsesquioxane
and hydrophilic monomer. Example of the solvent include, but not particularly limited
to, water, alcohols, ketones, esters, aliphatic hydrocarbons, halogenated hydrocarbons,
and other common organic solvents. In addition, when the monomer is a salt of an acid
monomer, solvents may be mixed and used, such as the addition of water for the purpose
of increase in solubility. However, since the porous supporting membrane is attacked
by the solvent in some cases depending on the type of the porous supporting membrane,
it is necessary to select a solvent which does not attack the porous supporting membrane.
[0032] In the polymer of the polyhedral silsesquioxane and hydrophilic monomer constituting
the separation function layer, the content of the hydrophilic monomer in the mixture
before the polymerization is preferably 10 to 99 weight% typically, depending on the
hydrophilicity of the hydrophilic monomer. The content of the hydrophilic monomer
controlled within this range can achieve desirable water permeability, separation
performance, and physical and chemical durability. On the other hand, when the content
of the hydrophilic monomer is too low, the degree of cross linkage of the separation
function layer is increased to densify the separation function layer, thereby easily
resulting in a decrease in the amount of a permeated substance. When the content is
too high, the separation function layer is at risk of swelling or dissolving more
with the solute to result in the inability to function as a separation function layer.
[0033] The separation function layer is preferably provided on at least one side of the
porous supporting membrane. While a plurality of separation function layers may be
provided, one separation function layer on one side is normally sufficient. The thickness
of the separation function layer is preferably 10 nm or more and 500 nm or less typically,
also depending on the pressure applied in use. The thickness of the separation function
layer controlled within this range can achieve desirable water permeability, separation
performance, and physical and chemical durability. On the other hand, when the separation
function layer is less than 10 nm, the mechanical strength will be decreased to give
rise to the possibility of decrease in durability and occurrence of defects. On the
contrary, when the separation function layer exceeds 500 nm, the permeability rate
of the permeated substance will be slowed down. The thickness of the separation function
layer can be measured by analyzing a scanning electron micrograph or a transmission
electron microscope. As the method for measuring the film thickness of the separation
function layer, there is the following method, for example. The composite separation
membrane with the base material peeled therefrom is cut in accordance with a freeze-fracture
method to obtain a sample for cross section observation. This sample can be coated
with thin platinum or platinum-palladium or ruthenium tetroxide for observation at
an accelerating voltageof3to6kV under a scanning electron microscope (FE-SEM). The
film thickness is determined from the obtained electron micrograph on the basis of
the observation magnification. The value of the film thickness of the separation function
layer in the present invention means the average value of measurements at 10 or more
points.
[0034] The porous supporting membrane according to the present invention is used as a supporting
membrane for the separation function layer in order to provide strength to the composite
separation membrane according to the present invention. Therefore, while the porous
supporting membrane is not particularly limited as long as the membrane has multiple
pores, the membrane preferably has substantially uniform pores or pores with their
pore sizes gradually increased from one side toward the other, and preferably has
a structure in which the surface on either side has a pore size of 100 nm or less.
Furthermore, the average pore size more preferably falls within the range of 1 to
100 nm. The average pore size of the porous supporting membrane controlled with in
this range can achieve desirable water permeability, separation performance, and physical
and chemical durability. On the other hand, when the average pore size falls below
1 nm, the permeation flux tends to decrease. When the average pore size exceeds 100
nm, the strength of the porous supporting membrane is likely to be decreased.
[0035] The average pore size can be obtained by, for example, observing a surface layer
of the porous supporting membrane at 60,000-fold magnification under a FE-SEM. More
specifically, an image shot under a FE-SEM is binarized to carry out an image analysis
and obtain the area of a pore section, and the obtained area of the pore section is
subjected to sphere approximation to recalculate a pore size. The pore size measurement
is carried out for 1,000 or more pores, and the average pore size is determined from
the respective pore sizes.
[0036] In addition, the porous supporting membrane preferably has a thickness within the
range of 1 µm to 5 mm, and more preferably within the range of 10 to 100 µm. The thickness
of the porous supporting membrane controlled within this range can provide desirable
physical and chemical durability and handling ability. On the other hand, the thickness
below 1 µm is likely to decrease the strength of the porous supporting membrane, whereas
the thickness exceeding 5 mm makes it more difficult to handle the porous supporting
membrane.
[0037] The membrane thickness of the porous supporting membrane herein can be obtained by
averaging values measured 10 or more times on a membrane thickness measuring apparatus
(for example, MITUTOYO No. 7050).
[0038] The porous supporting membrane has, as a base material, a nonwoven fabric composed
of a polyester fiber or a polyamide fiber or a cloth such as a plain weave fabric,
and has a porous layer formed on the base material. While the resin material used
for the porous layer is not particularly limited, homopolymers or copolymers such
as polysulfone, polyamide, polyester, cellulose based polymers, vinyl based polymers,
polyphenylene sulfide, polyphenylene sulfide sulfone, polyphenylene sulfone, and polyphenylene
oxide can be for example used singly or in combination. Among the polymers mentioned
above, it is preferable to use cellulose acetate, cellulose nitrate, etc., as a cellulose
based polymer, and polyethylene, polypropylene, polyvinyl chloride, polyacrylonitrile,
etc., as a vinyl based polymer. Above all, homopolymers or copolymers such as polysulfone,
polyamide, polyester, cellulose acetate, cellulose nitrate, polyvinyl chloride, polyacrylonitrile,
polyphenylene sulfide, polyphenylene sulfide sulfone are preferable. Furthermore,
among these materials, it is particularly preferable to use polysulfone which has
high chemical, mechanical, and thermal stability and is easy to mold.
[0039] The porous supporting membrane as described above can be obtained by, for example,
applying a dimethyl sulf oxide solution of polysulfone onto a base material such as
a polyester fiber to provide a substantially uniform thickness, and immersing the
base material with polysulfone applied in a water bath to remove the solvent.
[0040] The composite separation membrane according to the present invention can be formed
by applying a hydrophilic monomer solution containing the polyhedral silsesquioxane,
polymerization initiator, and hydrophilic monomer respectively at desirable ratios
by weight onto the surface of the porous supporting membrane obtained in accordance
with the method as described above, and polymerizing the hydrophilic monomer solution
by electromagnetic wave irradiation.
[0041] As the means for applying the hydrophilic monomer solution, there is a variety of
methods used conventionally, for example, dip coating, spin coating, spray coating,
brush coating, etc.
[0042] In the present invention, in the case of the separation membrane dried in the process
of polymerization by electromagnetic wave irradiation, a method may be combined for
carrying out a hydrophilicity imparting treatment with a hydrophilic agent as a post-treatment.
While the hydrophilic agent for use in the hydrophilicity imparting treatment is not
particularly limited as long as the hydrophilic agent has wettability to both water
and the separation membrane, a mixed solvent of water and alcohol is preferable in
terms of safety, cost, etc.
[0043] The time period of the hydrophilicity imparting treatment is typically about 10 minutes
in the case of carrying out the hydrophilicity imparting treatment at ordinary temperatures,
because all that is required is that the separation membrane is permeatedwi th the
hydrophilic agent. In this case, depending on the type of the membrane, the temperature
of hydrophilic agent may be increased to 40°C or more in order to enhance reduction
in time and the hydrophilic effect.
[Examples]
[0044] The present invention will be more specifically described below with reference to
examples. However, the present invention is not to be considered limited to these
examples. Special grade reagent products produced by Wako Pure Chemical Industries,
Ltd. were used for the regents, unless otherwise stated.
(Reference Example 1)
[0046] The porous supporting membrane reinforced with a fiber, used in the present invention,
was produced in accordance with the following approach.
[0047] Taffeta (150-denier multifilament yarn for both warp yarn and weft yarn, weaving
density: 90 yarns/inch in the length direction and 67 yarns/inch, thickness: 160µm)
composed of a 30 cm long × 20 cm wide polyester fiber was fixed to a glass plate,
and a 15 weight% dimethylformamide solution of polysulfone (Udel (Registered Trademark)
produced by Amoco, P-3500) was casted thereon at room temperature (25°C) to provide
a thickness of 200 µm, immediately followed by immersion in pure water and leaving
as it was for 5 minutes, thereby obtaining a porous supporting membrane. The pure
water permeation coefficient of the thus obtained porous supporting membrane was 0.005
to 0.01 kg/cm
2/sec/atm (about 0.001 to 0.002 g/cm
2/sec/MPa), which was measured at a pressure of 0.1 MPa and a temperature of 25°C.
In addition, the average pore size at the surface of the obtained porous supporting
membrane was 20 to 50 nm, and the thickness of the polysulfone moiety thereof was
50 µm.
(Example 1)
[0048] The porous supporting membrane produced in accordance with Reference Example 1 was
brought into contact with an isopropyl alcohol solution containing 3.6 weight% of
sodium styrenesulfonate, 0.4 weight% of Methacryl-POSS (polyhedral oligomeric silsesquioxane),
0.24 weight% of 2,2-dimethoxy-2-phenylacetophenone as an α-hydroxyacetophenone type
photopolymerization initiator, and 33. 5 weight% of pure water for 1 minute, and nitrogen
was sprayed from an air nozzle to remove the extra solution from the surface of the
porous supporting membrane, thereby forming a layer of the solution on the porous
supporting membrane. Then, with the use of an excimer lamp (UER 20-172) produced by
Ushio, inc., capable of irradiation with ultraviolet rays of 172 nm, the distance
between the excimer lamp and the porous supporting membrane was set to 1 cm under
a nitrogen atmosphere with an oxygen concentration of 0.1% or less, and irradiation
with ultraviolet rays was carried out for 5 minutes to produce a composite separation
membrane with a polymer of a polyhedral silsesquioxane and a hydrophilic monomer formed
on the surface of the porous supporting membrane. Then, immersion in a 10 weight%
isopropyl alcohol solution for 10 minutes was carried out for development of hydrophilicity.
The thickness of the thus obtained polymer was 250 nm on average according to confirmation
by UHR-FE-SEM. In addition, the thus obtained composite separation membrane was subjected
to a reverse osmosis test under the conditions of 0.5 MPa and 25°C, with the use of,
as raw water, a 500 ppm salt solution adjusted to pH 6,5 with hydrochloric acid or
sodium hydroxide, thereby obtaining the performance shown in Table 1 as the result
of the test. In addition, the thickness of the thus obtained polymer was 250 nm on
average according to confirmation by UHR-FE-SEM.
(Example 2)
[0049] A composite separation membrane was produced in the same way as in Example 1, except
that an isopropyl alcohol solution containing 1.8 weight% of an acrylic acid, 0.2
weight% of Methacryl-POSS, and 0.12 weight% of 2,2-dimethoxy-2-phenyl acetophenone
was used instead of the solution applied onto the porous supporting membrane in Example
1. The thus obtained composite separation membrane was evaluated in the same way as
in Example 1 to obtain the performance shown in Table 1.
(Comparative Example 1)
[0050] To the porous supporting membrane produced in accordance with Reference Example 1,
1.0 weight% of piperazine, 0.2 weight% of 1,3-di(4-piperidyl)propane, 0.5 weight%
of sodium alkyl diphenyl ether disulfonate, and 1.0 weight% of trisodium phosphate
were applied, followed by drying carried out with hot air at 70°C for 1 minute. Then,
an n-decane solution containing 0.4 weight% of isophthalic chloride and 0.1 weight%
of trimesic chloride was applied, followed by a treatment carried out with hot air
at 100°C for 5 minutes. Then, immersion in a 100 ppm chlorine solution adjusted to
pH 7 was further carried out for 2minutes, followed by washing with pure water. The
thus obtained composite separation membrane was evaluated in the same way as in Example
1 to obtain the performance shown in Table 1.
(Comparative Example 2)
[0051] A composite separation membrane was produced in the same way as in Example 1, except
that the Methacryl-POSS in the solution applied onto the porous supporting membrane
in Example 1 was changed to divinylbenzene. The thus obtained composite separation
membrane was evaluated in the same way as in Example 1 to obtain the performance shown
in Table 1.
[0052] The composite separation membranes according to Examples 1 to 2 and Comparative Examples
1 to 2 were immersed in a 500 ppm chlorine solution adjusted to pH 7 for 1 week to
carry out a chemical resistant test. The results are shown in Table 1.
[0053] It is determined from Table 1 that the composite separation membranes according to
the present invention have excellent chemical resistance in addition to excellent
separation performance and water permeability.
[Table 1]
|
Initial Performance |
Performance Retention Rate after Immersion in Chlorine (%) |
Removal Rate (%) |
Permeability Rate (m3/m2/day) |
Example 1 |
62.3 |
2.52 |
105 |
Example 2 |
81.4 |
0.82 |
98 |
Comparative Example 1 |
65.5 |
1.10 |
55 |
Comparative Example 2 |
27.6 |
5.76 |
101 |